CN111978540B - High-temperature dielectric energy storage application of copolymer-based nanocomposite - Google Patents
High-temperature dielectric energy storage application of copolymer-based nanocomposite Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 75
- 229920001577 copolymer Polymers 0.000 title claims abstract description 71
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000004642 Polyimide Substances 0.000 claims abstract description 34
- 229920001721 polyimide Polymers 0.000 claims abstract description 34
- 239000004952 Polyamide Substances 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 26
- 229920002647 polyamide Polymers 0.000 claims abstract description 26
- 229910052582 BN Inorganic materials 0.000 claims abstract description 24
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002135 nanosheet Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims description 90
- 229920005575 poly(amic acid) Polymers 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 abstract description 40
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 13
- 239000011232 storage material Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013339 polymer-based nanocomposite Substances 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides a copolymer for high-temperature dielectric energy storage and a nanocomposite thereof, comprising a base material and hexagonal boron nitride nano-sheets dispersed in the base material; the base material is polyimide-polyamide acid copolymer, and the mole percentage content of polyimide in the copolymer is 10% -90%. Compared with the prior art, the nanocomposite provided by the invention uses the copolymer as a base material, and the polyimide and polyamide acid mole percentage content is regulated and controlled through imidization, so that the nanocomposite has high breakdown field strength and high energy density; meanwhile, the boron nitride nanosheets dispersed in the copolymer substrate have the characteristics of high heat conductivity, high insulativity and large length-diameter ratio, and can effectively improve the breakdown field intensity and the energy storage efficiency of the nanocomposite at high temperature, so that the copolymer-based nanocomposite which can be used for dielectric energy storage, in particular to the application in the field of high-temperature dielectric energy storage is obtained.
Description
Technical Field
The invention belongs to the technical field of dielectric energy storage materials, and particularly relates to a copolymer and a nanocomposite for high-temperature dielectric energy storage and a preparation method thereof.
Background
The research of the energy storage material has important scientific significance and application value. Compared with the energy storage performance of super capacitor, lithium ion battery and the like, the dielectric energy storage capacitor has higher power density and is very suitable for being applied to the fields of hybrid electric vehicles, aerospace and the like. Among them, the flexible polymer and polymer-based nanocomposite material which is resistant to high voltage and easy to process is one of the dielectric energy storage materials with the most application potential.
However, the loss of the polymer dielectric medium increases exponentially with the increase of temperature, so that the performances of the polymer material capacitor such as breakdown field strength, energy storage density, energy storage efficiency and the like are reduced at high temperature, and the requirement of stable operation in a high-temperature environment cannot be met. For example, biaxially oriented polypropylene (BOPP) film, which is currently widely used in hybrid vehicles, is a flexible polymeric material that typically operates at temperatures below 105 ℃ and ambient temperatures near the vehicle engine of 140 ℃ -150 ℃ (y. Zhou and q. Wang, advanced polymer dielectrics for high temperature capacitive energy storage, journal of Applied Physics,2020,127 (24), 240902). In order to make BOPP film capacitor work normally, it needs to equip corresponding cooling device, which causes waste of space and energy. Moreover, BOPP materials have low relative dielectric constants (about 2.2), and therefore have low recyclable energy densities at room temperature, typically less than 2J/cm 3 (B.Liu, M.H.Yang, W.Y.Zhou, H.W.Cai, S.L.Zhong, M.S.Zheng and Z.M. Dang, high energy density and discharge efficiency polypropylene nanocomposites for potential high-power capacitor, energy Storage Materials,2020,27,443-452.). Therefore, we need to obtain polymer-based nanocomposite materials that can be applied in high temperature environment, so that they have higher breakdown field strength, energy density and energy storage efficiency on the basis of high temperature resistance, and at the same time have lower production cost.
Based on high-temperature resistant and low-cost polymer materials, the construction of the nanocomposite material by adding inorganic nano fillers is to optimize the high-temperature dielectric storageImportant strategies for energy performance. For example, ai et al increased the breakdown field strength at 150℃from lower 314MV/m to 422MV/m by adding nano additives such as alumina, boron nitride, etc. to polyimide polymer. However, the polymer matrix material has poor dielectric energy storage performance, and the maximum energy storage density of the base material at 250MV/m is only 0.82J/cm at 150 DEG C 3 The corresponding energy storage efficiency is also only 55.7% (D.Ai, H.Li, Y.Zhou, L.L.Ren, Z.B.Han, B.Yao, W.Zhou, L.Zhao, J.M.Xu and q. Wang, tuning Nanofillers in In Situ Prepared Polyimide Nanocomposites for High-Temperature Capacitive Energy Storage, advanced Energy Materials,2020,10 (16), 1903881.).
There is currently no polymer-based dielectric energy storage material that can be used at high temperatures. It is expected that designing and preparing a novel polymer matrix material with high temperature resistance, high breakdown field strength and high energy density, combined with applying a corresponding nano additive strategy, will be able to significantly improve the high temperature dielectric energy storage characteristics of the material. The invention of the design and the preparation method of the novel polymer material capable of being used for high-temperature dielectric energy storage is one of the core problems of realizing high-quality high-temperature dielectric energy storage.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polymer with high breakdown field strength and high energy density, a nanocomposite dielectric energy storage material based on the polymer, and a preparation method thereof.
The invention provides a polyimide-polyamide acid copolymer for high-temperature dielectric energy storage; the polyimide-polyamide acid copolymer contains polyimide in 10-90 mol%.
Preferably, the polyimide-polyamic acid copolymer is prepared according to the following method:
mixing a polyamic acid solution with a solvent to obtain a mixture solution;
casting and heating the mixture solution to obtain polyimide-polyamide acid copolymer;
the temperature of the heating does not exceed 300 ℃.
The invention also provides a nanocomposite for high-temperature dielectric energy storage, which comprises a base material and hexagonal boron nitride nano sheets dispersed in the base material;
the substrate is polyimide-polyamide acid copolymer;
the polyimide-polyamide acid copolymer contains polyimide in 10-90 mol%.
Preferably, the polyimide-polyamide acid copolymer comprises 30-60% of polyimide in mole percent;
the volume percentage of the hexagonal boron nitride nano-sheet in the nano-composite material is more than 0 and less than or equal to 1 percent.
Preferably, the nanocomposite is prepared according to the following method:
mixing a polyamic acid solution, a proper amount of hexagonal boron nitride nano-sheets and a solvent to obtain a mixture solution;
casting and heating the mixture solution to obtain a nanocomposite;
the heating temperature does not exceed 300 ℃.
Preferably, the heating is stepwise heating; the number of steps of the step-by-step heating is 2-5.
Preferably, the heating step specifically includes:
maintaining at 70-90 deg.c for 10-30 min, heating to 110-130 deg.c for 20-40 min, and heating to 150-170 deg.c for 20-40 min.
Preferably, the heating step specifically includes:
maintaining at 70-90 deg.c for 10-30 min, heating to 110-130 deg.c for 20-40 min, heating to 150-170 deg.c for 20-40 min, and heating to 180-230 deg.c for 30-80 min.
Preferably, the heating step specifically includes:
the temperature is kept at 80 ℃ for 20min, then the temperature is raised to 120 ℃ for 30min, then the temperature is raised to 160 ℃ for 30min, and finally the temperature is raised to 200 ℃ for 60min.
The invention also provides application of the polyimide-polyamide acid copolymer material or the nanocomposite material as a dielectric energy storage material, in particular to application of the high-temperature resistant dielectric energy storage material.
The invention provides a Polyimide (PI) -polyamide acid (PAA) copolymer material for dielectric energy storage; the polyimide-polyamide acid copolymer contains polyimide in 10-90 mol%. Compared with the prior art, the copolymer provided by the invention realizes the regulation and control of the mole percentages of PI and PAA through imidization, so that the copolymer shows high breakdown field strength and high energy density, and can be used as a dielectric energy storage material.
Further, the invention also provides a nanocomposite material for dielectric energy storage, in particular for high-temperature dielectric energy storage, comprising a substrate and hexagonal Boron Nitride Nanoplatelets (BNNS) dispersed in the substrate; the substrate is polyimide-polyamide acid copolymer; the polyimide-polyamide acid copolymer contains polyimide in 10-90 mol%. Compared with the prior art, the nanocomposite provided by the invention uses polyimide-polyamide acid copolymer as a base material, and realizes the regulation and control of the mole percentages of PI and PAA through imidization, so that the nanocomposite shows high breakdown field strength and high energy density; meanwhile, the boron nitride nanosheets dispersed in the copolymer substrate have the characteristics of high heat conductivity, high insulativity and large length-diameter ratio, and can effectively improve the breakdown field intensity and the energy storage efficiency of the composite material at high temperature, so that the nanocomposite material which can be applied to the field of high-temperature dielectric energy storage is obtained.
Experimental results show that the breakdown field of the 0.54PI-0.46PAA copolymer substrate with 54% PI mole percentage prepared at the final heating temperature of 200 ℃ at room temperature is more than 620MV/m, and the energy density is more than 8.0J/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The breakdown field strength of the 0.54PI-0.46PAA copolymer substrate is 517MV/m and the energy density is 4.4J/cm under the high temperature environment of 150 DEG C 3 The method comprises the steps of carrying out a first treatment on the surface of the When 0.1vol% BNNS is added, the breakdown field strength and energy density of the copolymer substrate are further improved: under the high temperature environment of 150 ℃, the breakdown field strength is 527MV/m, and the energy density is 7.8J/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The copolymer-based nanocomposite provided by the invention still has high breakdown field strength and high energy density at a high temperature of 150 ℃.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a nanocomposite dielectric energy storage material according to the present invention;
FIG. 2 is a graph showing the results of testing the breakdown field strength of the polyimide-polyamic acid copolymers obtained in examples 1 to 5 of the present invention;
FIG. 3 is a graph showing the results of measuring the energy density and the energy storage efficiency of the polyimide-polyamic acid copolymer obtained in examples 1 to 5 according to the present invention at room temperature;
FIG. 4 is a Fourier transform infrared spectrum of the polyimide-polyamic acid copolymer obtained in examples 1 to 5 of the present invention, and a molar percentage of polyimide in the corresponding copolymer;
FIG. 5 is a graph showing the results of energy density and energy storage efficiency at 150℃for the copolymer substrate of example 3 and nanocomposite of example 6 according to the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a polyimide-polyamide acid copolymer material for dielectric energy storage; the polyimide-polyamide acid copolymer contains polyimide in the molar percentage of 10-90%, preferably 15-85%, more preferably 30-60%, and most preferably 54%.
In the present invention, the polyimide-polyamic acid copolymer is preferably prepared according to the following method: mixing a polyamic acid solution with a solvent to obtain a mixture solution; casting and heating the mixture solution to obtain polyimide-polyamide acid copolymer; the heating temperature is not more than 300 ℃.
The source of all the raw materials is not particularly limited, and the raw materials are commercially available.
In the present invention, the polyamic acid solution may be synthesized from dianhydride or tetracarboxylic acid and diamine, and is not particularly limited, but is preferably synthesized from 4,4' -bis (3-aminophenoxy) diphenylsulfone (m-BAPS) and pyromellitic dianhydride (PMDA); the solid content of the polyamic acid solution is preferably 10% to 20%, and most preferably 20%.
Mixing a polyamic acid solution with a solvent to obtain a mixture solution; the solvent is preferably one or more of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC) and N-methylpyrrolidone (NMP); the volume ratio of the polyamic acid solution to the solvent is preferably 1: (1 to 20), most preferably 1:7.
casting and heating the mixture solution to obtain polyimide-polyamide acid copolymer; the final temperature of the heating is preferably 110 ℃ to 280 ℃, more preferably 160 ℃ to 250 ℃; the heating is preferably a stepwise heating; the number of steps of the stepwise heating is preferably 2 to 5, more preferably 3 to 4.
Wherein, when the final heating temperature is 110 ℃ to 130 ℃, the number of steps of the step-by-step heating is preferably 2 steps; the heating is preferably specifically: maintaining at 70-90 deg.c for 10-30 min, and raising the temperature to 110-130 deg.c for 20-40 min; more preferably, the temperature is kept between 75 and 85 ℃ for 15 to 25 minutes, and then the temperature is raised to between 115 and 125 ℃ and kept for 25 to 35 minutes; it is further preferable that the temperature is 80℃for 20min, and then the temperature is raised to 120℃for 30min.
When the final heating temperature is 150-170 ℃, the number of steps of the step heating is preferably 3; the heating is preferably specifically: maintaining at 70-90 deg.c for 10-30 min, heating to 110-130 deg.c for 20-40 min, heating to 150-170 deg.c for 20-40 min; more preferably, the temperature is 75-85 ℃ for 15-25 min, then the temperature is raised to 115-125 ℃ for 25-35 min, and then the temperature is raised to 155-165 ℃ for 25-35 min; it is further preferable that the temperature is 80℃for 20min, then the temperature is raised to 120℃for 30min, and then the temperature is raised to 160℃for 30min.
When the final heating temperature is 180-230 ℃, the number of steps of the step-by-step heating is preferably 4 steps; the heating is preferably specifically: maintaining at 70-90 deg.c for 10-30 min, heating to 110-130 deg.c for 20-40 min, heating to 150-170 deg.c for 20-40 min, and heating to 180-250 deg.c for 30-80 min; more preferably, the temperature is 75-85 ℃ for 15-25 min, then the temperature is raised to 115-125 ℃ for 25-35 min, then the temperature is raised to 155-165 ℃ for 25-35 min, and finally the temperature is raised to 180-220 ℃ for 40-70 min; it is further preferable that the temperature is 80 ℃ for 20min, then the temperature is raised to 120 ℃ for 30min, then the temperature is raised to 160 ℃ for 30min, and finally the temperature is raised to 200 ℃ for 60min.
When the final heating temperature is 240-280 ℃, the number of steps of the step heating is preferably 5 steps; the heating is preferably specifically: maintaining at 70-90 deg.c for 10-30 min, heating to 110-130 deg.c for 20-40 min, heating to 150-170 deg.c for 20-40 min, heating to 180-230 deg.c for 30-80 min, and heating to 240-280 deg.c for 20-40 min; more preferably, the temperature is kept between 75 and 85 ℃ for 15 to 25 minutes, then the temperature is raised to 115 to 125 ℃ for 25 to 35 minutes, then the temperature is raised to 155 to 165 ℃ for 25 to 35 minutes, then the temperature is raised to 180 to 220 ℃ for 40 to 70 minutes, and finally the temperature is raised to 250 to 260 ℃ for 25 to 35 minutes; preferably, the temperature is 80 ℃ for 20min, then the temperature is raised to 120 ℃ for 30min, then the temperature is raised to 160 ℃ for 30min, then the temperature is raised to 200 ℃ for 60min, and finally the temperature is raised to 250 ℃ for 30min.
In the present invention, the temperature rise rate is preferably 1 to 10℃per minute, and most preferably 6℃per minute.
The copolymer provided by the invention realizes the regulation and control of the mole percentages of PI and PAA through imidization, thereby showing high breakdown field strength and high energy density, and further being applicable to dielectric energy storage materials.
The invention also provides a nanocomposite material for dielectric energy storage, in particular for high-temperature dielectric energy storage, which comprises a base material and hexagonal boron nitride nanoplatelets dispersed in the base material; the substrate is polyimide-polyamide acid copolymer; the polyimide-polyamide acid copolymer contains polyimide in 10-90 mol%.
The thickness of the substrate is preferably 5 to 50 μm; the substrate is polyimide-polyamide acid copolymer; the polyimide-polyamide acid copolymer contains polyimide in the molar percentage of 10-90%, preferably 15-85%, more preferably 30-60%, and most preferably 54%.
Hexagonal boron nitride nanosheets are dispersed in the base material, and the hexagonal boron nitride nanosheets are used as inorganic nano fillers and have the characteristics of high heat conductivity, high insulativity and large length-diameter ratio. The volume percentage of the hexagonal boron nitride nano-sheet in the nano-composite material is preferably more than 0 and less than or equal to 1%, more preferably 0.05-1%, still more preferably 0.05-0.5%, still more preferably 0.1-0.5%, and most preferably 0.1%; the hexagonal boron nitride nanosheets in the nanocomposite have a low content, and are beneficial to being uniformly dispersed in the base material.
The nanocomposite provided by the invention uses polyimide-polyamide acid copolymer as a base material, and has a specific mole percentage so as to show high breakdown field strength and high energy density; meanwhile, the boron nitride nanosheets dispersed in the copolymer substrate have the characteristics of high heat conductivity, high insulativity and large length-diameter ratio, and can effectively improve the breakdown field intensity and the energy storage efficiency of the nanocomposite at high temperature, so that the copolymer-based nanocomposite which can be applied to the field of high-temperature dielectric energy storage is obtained.
The invention also provides a preparation method of the nanocomposite, which comprises the following steps: mixing a polyamic acid solution, hexagonal boron nitride nano-sheets and a solvent to obtain a mixture solution; casting and heating the mixture solution to obtain a nanocomposite; the heating temperature does not exceed 300 ℃.
Referring to fig. 1, fig. 1 is a schematic diagram of a nanocomposite preparation process provided by the present invention.
The source of all the raw materials is not particularly limited, and the raw materials are commercially available.
In the present invention, the polyamic acid solution may be synthesized from dianhydride or tetracarboxylic acid and diamine, and is not particularly limited, but is preferably synthesized from 4,4' -bis (3-aminophenoxy) diphenylsulfone (m-BAPS) and pyromellitic dianhydride (PMDA); the solid content of the polyamic acid solution is preferably 10% to 20%, and most preferably 20%.
Firstly, mixing a polyamic acid solution with a solvent, and then adding hexagonal boron nitride nano-sheets for mixing to obtain a mixture solution; the method of mixing after adding the hexagonal boron nitride nano-sheets is preferably magnetic stirring.
Casting and heating the mixture solution to obtain a nanocomposite; the heating process is the same as the heating process of the copolymer matrix, the heating process is step-by-step heating, and the imidization degree of the base material is regulated and controlled through heating, namely the regulation and control of the mole percentage content of PI and PAA are realized. The final temperature of the heating is preferably 180 ℃ to 230 ℃, more preferably 180 ℃ to 220 ℃, most preferably 200 ℃; the heating is preferably a stepwise heating; the number of steps of the stepwise heating is most preferably 4. The most preferred heating process is as follows:
when the final heating temperature is 180-230 ℃, the number of steps of the step-by-step heating is preferably 4 steps; the heating is preferably specifically: maintaining at 70-90 deg.c for 10-30 min, heating to 110-130 deg.c for 20-40 min, heating to 150-170 deg.c for 20-40 min, and heating to 180-250 deg.c for 30-80 min; more preferably, the temperature is 75-85 ℃ for 15-25 min, then the temperature is raised to 115-125 ℃ for 25-35 min, then the temperature is raised to 155-165 ℃ for 25-35 min, and finally the temperature is raised to 180-220 ℃ for 40-70 min; it is further preferable that the temperature is 80 ℃ for 20min, then the temperature is raised to 120 ℃ for 30min, then the temperature is raised to 160 ℃ for 30min, and finally the temperature is raised to 200 ℃ for 60min.
In the present invention, the temperature rise rate is preferably 1 to 10℃per minute, more preferably 6℃per minute.
According to the invention, the final heating temperature is changed to adjust the mole percentage of PI and PAA in the xPI- (1-x) PAA (x is the mole percentage of polyimide in the copolymer) copolymer material, so that the physical properties of the polyimide copolymer material are adjusted. The xPI- (1-x) PAA copolymer substrates of the present invention have significantly improved breakdown strength and energy storage density due to a wider band gap, higher dielectric constant compared to PI substrates, as compared to polyimide materials typically prepared at greater than 300 ℃. The boron nitride nano-sheets uniformly dispersed in the copolymer substrate have the characteristics of high heat conductivity, high insulativity and large length-diameter ratio, and can further improve the breakdown field strength and the energy storage efficiency of the composite material at high temperature. Therefore, the nanocomposite material has the characteristics of high breakdown field strength and high energy density at high temperature, and has important industrial application value in the field of high-temperature dielectric energy storage.
In order to further illustrate the present invention, the following describes in detail a copolymer for dielectric energy storage, a nanocomposite material and a preparation method thereof according to examples.
The reagents used in the examples below are all commercially available.
Hexagonal boron nitride: provided by Shanghai Ala Biochemical technology Co., ltd, the purity was 99.9%;
PAA solution: is provided by Hezhou Furun plastic new material Co., ltd, and the solid content is 20%;
n, N-dimethylacetamide solvent: provided by the national pharmaceutical group chemical reagent company, the purity is more than or equal to 99.0 percent;
premier type II hysteresis loop test system: the manufacturer: radio (united states) for measuring breakdown field strength, energy density and energy storage efficiency, test temperature: the electrodes of the capacitor samples were gold (Au) electrodes with a diameter of 2 millimeters (mm) at room temperature and 150 c, and the thickness of the composite material was about 13-15 μm.
Example 1: preparation of 0.15PI-0.85PAA copolymer substrate
3mL of the PAA solution was mixed with 21mL of DMAC solvent, and stirred with a magnetic stirrer for 12 hours to obtain a mixed solution.
3mL of the mixed solution was slowly spread on a leveled clean quartz glass substrate, and then DMAC solvent was removed by staged heating while imidizing PAA.
The specific heating process is as follows:
raising the temperature to 80 ℃ at a rate of 6 ℃/min and holding for 20min; the temperature was then raised to 120℃and maintained for 30min.
Example 2: preparation of 0.32PI-0.68PAA copolymer substrate
The substrate of this example was prepared in the same manner as in example 1, except that the heating process was as follows:
raising the temperature to 80 ℃ at a rate of 6 ℃/min and holding for 20min; then the temperature is raised to 120 ℃ and kept for 30min; the temperature was further raised to 160℃and maintained for 30min.
Example 3: preparation of 0.54PI-0.46PAA copolymer substrate
The substrate of this example was prepared in the same manner as in example 1, except that the heating process was as follows:
raising the temperature to 80 ℃ at a rate of 6 ℃/min and holding for 20min; then the temperature is raised to 120 ℃ and kept for 30min; further heating to 160deg.C and maintaining for 30min; finally, the temperature was raised to 200℃and maintained for 60min.
Example 4: preparation of 0.85PI-0.15PAA copolymer substrate
The substrate of this example was prepared in the same manner as in example 1, except that the heating process was as follows:
raising the temperature to 80 ℃ at a rate of 6 ℃/min and holding for 20min; then the temperature is raised to 120 ℃ and kept for 30min; further heating to 160deg.C and maintaining for 30min; then the temperature is raised to 200 ℃ and kept for 60min; finally, the temperature was raised to 250℃and maintained for 30min.
Example 5 preparation of PI substrate
The substrate of this example was prepared in the same manner as in example 1, except that the heating process was as follows:
raising the temperature to 80 ℃ at a rate of 6 ℃/min and holding for 20min; then the temperature is raised to 120 ℃ and kept for 30min; further heating to 160deg.C and maintaining for 30min; then the temperature is raised to 200 ℃ and kept for 60min; subsequently the temperature was raised to 250 ℃ and maintained for 30min; finally, the temperature was raised to 300℃and maintained for 30min.
Example 6: preparation of 0.54PI-0.46PAA+y vol% BN copolymer-based nanocomposite
The copolymer-based nanocomposite of this example was prepared in the same manner as in example 3, except that the boron nitride nanoplatelets were added in the mixed solution in the proportions of 0.05vol%, 0.1vol%, 0.5vol% and 1vol%, respectively, of the copolymer-based nanocomposite. Furthermore, the composite material obtained when the volume ratio of the boron nitride nano-sheets in the whole copolymer-based nano composite material is 0.1 percent has the highest breakdown field strength and energy storage density.
Test case
This test example measures the breakdown field strength, energy density and energy storage efficiency of each of the substrates of examples 1 to 5 at room temperature, and the copolymer substrate of example 3 and the copolymer-based nanocomposite of example 6 at 150 ℃ with a test frequency of 10Hz.
The results of the breakdown field strength tests of examples 1 to 5 are shown in fig. 2, and the energy density and energy storage efficiency test results of examples 1 to 5 at room temperature are shown in fig. 3. According to the results, the 0.15PI-0.85PAA copolymer substrate of example 1 had a breakdown field strength of 308MV/m and an energy density of 1.3J/cm at room temperature 3 The energy storage efficiency corresponding to 200MV/m field intensity is 56.2%; the 0.32PI-0.68PAA copolymer substrate of example 2 had a breakdown field strength of 408MV/m and an energy density of 3.3J/cm at the breakdown field strength 3 The energy storage efficiency corresponding to the field intensity of 200MV/m is 92.4 percent, and the energy storage efficiency corresponding to the field intensity of 400MV/m is 34.2 percent; the 0.54PI-0.46PAA copolymer substrate of example 3 had a breakdown field strength of 627MV/m and an energy density of 8.1J/cm at the breakdown field strength 3 The energy storage efficiency corresponding to 200MV/m field intensity is 96.3 percent, and the energy storage efficiency corresponding to 400MV/m field intensity is 91.2 percent; the 0.85PI-0.15PAA copolymer substrate of example 4 had a breakdown field strength of 517MV/m and an energy density of 6.5J/cm at breakdown field strength 3 The energy storage efficiency corresponding to 200MV/m field intensity is 91.8%, and the energy storage efficiency corresponding to 400MV/m field intensity is 88.5%; the PI substrate of example 5 had a breakdown field strength of 467MV/m and an energy density of 5.8J/cm at breakdown field strength 3 The energy storage efficiency corresponding to 200MV/m field intensity is 96.1%, and the energy storage efficiency corresponding to 400MV/m field intensity is 87.5%.
The fourier transform infrared spectra of examples 1 to 5 and the mole percentage of polyimide in the corresponding copolymers are shown in fig. 4. The results show that as the final heating temperature of the substrate increases from 120 ℃ to 300 ℃, PAA (PThe characteristic peaks of AA are marked by dotted boxes in the figure and are located at 1660cm respectively -1 And 1550cm -1 Position) gradually changed into PI (infrared characteristic peak of PI is marked by arrow in the figure, and is respectively located at 1778cm -1 、1728cm -1 、1371cm -1 And 725cm -1 ). The characteristic infrared absorption peak of PAA was still present at a final heating temperature of 200 ℃ at which the molar percentage of PI in the substrate was 54%.
FIG. 5 is a graph showing the results of energy density and energy storage efficiency tests at 150℃for the copolymer substrate of example 3 and the copolymer-based nanocomposite of example 6 according to the present invention. Breakdown field strength of 0.54PI-0.46PAA+0.1vol% BN material is 527MV/m, energy density and energy storage efficiency corresponding to the field strength are 7.8J/cm respectively 3 And 56%; the breakdown field strength of the 0.54PI-0.46PAA copolymer is 517MV/m, and the energy density and the efficiency corresponding to the field strength are 4.4J/cm respectively 3 And 14%. Therefore, the addition of a proper amount of BNNS can effectively improve the breakdown field strength, the energy density and the energy storage efficiency of the xPI- (1-x) PAA copolymer at high temperature. Further, for 0.54PI-0.46PAA+0.1vol% BN material, the energy density and energy storage efficiency at 150℃and 200MV/m are 1.39J/cm, respectively 3 And 97.2%, which has exceeded the energy density of BOPP material at room temperature and 200MV/m (0.39J/cm) 3 ) And energy storage efficiency (96.7%). The copolymer-based nanocomposite of the present invention can be applied to the field of high temperature dielectric energy storage applications, such as hybrid vehicles.
In summary, in one aspect, the present invention provides a copolymer substrate having a specific PI mole percent by adjusting the preparation temperature, adjusting the mole percent of polyimide in the xPI- (1-x) PAA copolymer substrate, and having a high breakdown field strength and a high energy density at room temperature. On the other hand, by adding a proper amount of BNNS, the energy storage performance of the polymer at high temperature is further improved, and finally, the copolymer-based nanocomposite which can normally work at high temperature (150 ℃) and has high breakdown field strength and high energy density is invented, so that the problem that the current commercial polymer capacitor cannot work at high temperature is hopefully solved.
Claims (7)
1. The nanocomposite for high-temperature dielectric energy storage is characterized by comprising a base material and hexagonal boron nitride nano-sheets dispersed in the base material;
the substrate is polyimide-polyamide acid copolymer;
the polyimide in the polyimide-polyamide acid copolymer accounts for 30-60 percent by mole;
the volume percentage of the hexagonal boron nitride nano-sheet in the nano-composite material is more than 0 and less than or equal to 1 percent.
2. The nanocomposite for high temperature dielectric energy storage according to claim 1, wherein the polyimide-polyamic acid copolymer is prepared according to the following method:
mixing a polyamic acid solution with a solvent to obtain a mixture solution;
casting and heating the mixture solution to obtain polyimide-polyamide acid copolymer;
the temperature of the heating does not exceed 300 ℃.
3. The nanocomposite for high temperature dielectric energy storage according to claim 1, wherein the nanocomposite is prepared according to the following method:
mixing a polyamic acid solution, a proper amount of hexagonal boron nitride nano-sheets and a solvent to obtain a mixture solution;
casting and heating the mixture solution to obtain a nanocomposite;
the heating temperature does not exceed 300 ℃.
4. The nanocomposite for high temperature dielectric energy storage of claim 3, wherein the heating is a step-wise heating; the number of steps of the step-by-step heating is 2-5.
5. The nanocomposite for high temperature dielectric energy storage according to claim 3, wherein the heating step is specifically:
maintaining at 70-90 deg.c for 10-30 min, heating to 110-130 deg.c for 20-40 min, and heating to 150-170 deg.c for 20-40 min.
6. The nanocomposite for high temperature dielectric energy storage according to claim 3, wherein the heating step is specifically:
maintaining at 70-90 deg.c for 10-30 min, heating to 110-130 deg.c for 20-40 min, heating to 150-170 deg.c for 20-40 min, and heating to 180-230 deg.c for 30-80 min.
7. A nanocomposite according to claim 3, wherein the step of heating is in particular:
the temperature is kept at 80 ℃ for 20min, then the temperature is raised to 120 ℃ for 30min, then the temperature is raised to 160 ℃ for 30min, and finally the temperature is raised to 200 ℃ for 60min.
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